V. Kriegisch, C. Lambert
FULL PAPER
94.2, 90.8 ppm. C22H12N2O6·H2O (418.35): calcd. C 63.16, H 3.37,
1,2-Bis(tert-butyldimethylsilyloxy)-4,5-bis{2-[4-(trimethylammonio)-
phenyl]ethynyl}benzene Diiodide (13): To a solution of 1,2-bis(tert-
N 6.70; found C 63.51, H 3.49, N 6.41. IR (KBr): ν = 3480 (br.,
˜
O–H), 3046 (vw, aryl-C–H), 2204 (m, CϵC), 1590 (s), 1508 (s, butyldimethylsilyloxy)-4,5-bis{2-[4-(dimethylamino)phenyl]-
NO2), 1441 (vw), 1349 (s, NO2), 1308 (m), 1261 (w), 1182 (w), 1145
ethynyl}benzene (12; 1.45 g, 2.31 mmol) in THF (20 mL) methyl
iodide (5 mL) was added. The reaction mixture was sealed in a
Schlenk tube and heated to 55 °C for 4 d. Excess methyl iodide
and the solvent were removed in vacuo. The light yellow solid was
dissolved in acetone by heating the mixture to 40 °C, n-hexane was
added and the acetone was removed in a rotary evaporator. The
precipitate was filtered off and washed twice with n-hexane to yield
(w), 1074 (vw), 848 (m), 749 (w), 686 (vw) cm–1.
Dilithium Tris{4,5-bis[2-(4-nitrophenyl)ethynyl]-1,2-benzenediolato}-
titanate(IV) (9): To a mixture of 1,2-dihydroxy-4,5-bis[2-(4-nitro-
phenyl)ethynyl]benzene (8; 50.0 mg, 125 µmol) and Li2CO3
(3.10 mg, 41.9 µmol) in dry MeOH (10 mL) TiO(acac)2 (10.9 mg,
41.5 µmol) was added. The solution turned deep red and was
stirred at room temperature for 24 h. The solvent was removed in
vacuo, the red solid was dissolved in THF and Et2O and carefully
covered with a layer of petroleum ether. Overnight a red solid crys-
tallised which was filtered off and recrystallised from MeCN. Yield
1
a colourless solid. Yield 86% (1.78 g). H NMR (250 MHz, [D6]-
DMSO, 25 °C): δ = 8.06–8.03 (4 H), 7.79–7.74 (4 H), 7.11–7.00 (2
H, 3-H, 6-H), 3.64 (18 H, Me3N), 0.98–0.83 [18 H, (CH3)3CSi],
0.25 to –0.04 [12 H, (CH3)2Si] ppm. 13C NMR (62.9 MHz, [D6]-
DMSO, 25 °C): δ = 147.78, 146.78, 132.51, 132.42, 132.34, 132.24,
124.10, 123.91, 121.29, 121.24, 118.10, 90.26, 89.60, 56.41, 56.34,
25.50, 25.32, 25.26, 18.15, 18.13, 17.72, –3.24, –4.26, –4.54 ppm.
C40H58I2N2O2Si2 (908.89): calcd. C 52.86, H 6.43, N 3.08; found
1
88% (49.0 mg) of a red solid. H NMR (250 MHz, [D4]methanol,
25 °C): δ = 8.25 (AAЈ, 12 H), 7.68 (BBЈ, 12 H), 6.62 (s, 6 H, 3-H,
6-H) ppm. 13C NMR (62.9 MHz, [D4]methanol, 295 K): δ = 161.6,
147.6, 132.5, 132.2, 124.5, 116.4, 115.4, 96.7, 89.9 ppm.
C66H36Li2N6O18Ti·4H2O (1328.86): calcd. C 59.66, H 2.88, N 6.32;
C 52.59, H 6.18, N 3.11. IR (KBr): ν = 3013 (vw, C–H-aryl), 2955
˜
(w, C–H), 2929 (w, C–H), 2885 (vw, C–H), 2857 (w, N–Me), 2210
(vw, CϵC), 1532 (m), 1513 (s), 1492 (m), 1471 (w), 1407 (w), 1357
(m), 1254 (s), 1117 (vw), 1082 (vw), 1013 (vw), 934 (s), 887 (w),
840 (s), 804 (w), 783 (m), 687 (vw), 564 (vw) cm–1.
found C 59.41, H 2.58, N 6.16. IR (KBr): ν = 3056 (vw, aryl-
˜
C–H), 2196 (m, CϵC), 1592 (m, NO2), 1509 (m), 1498 (m), 1477
(m), 1341 (s, NO2), 1241 (s, C–O), 1106 (w), 887 (w), 850 (w), 792
(w), 748 (w), 705 (vw), 687 (vw), 613 (w) cm–1.
Tris(4,5-bis{2-[4-(trimethylammonio)phenyl]ethynyl}-1,2-benzenedi-
olato)titanium(IV) Tetraiodide (14): To a solution of 1,2-bis(tert-bu-
tyldimethylsilyloxy)-4,5-bis{2-[4-(trimethylammonio)phenyl]-
ethynyl}benzene diiodide (13; 200 mg, 220 µmol) in dry MeOH
(13 mL) was added nBu4NF (151 mg, 578 µmol, 1 solution in
THF) followed by TiO(acac)2 (19.2 mg, 73.2 µmol). The solution
turned red and was stirred at room temperature for 24 h. The
orange precipitate was filtered off and washed carefully with
MeOH. The solid was suspended in MeOH (15 mL) and the sus-
pension added dropwise to a concd. solution of NH4(PF6) in
MeOH (10 mL). The precipitate was filtered off and the procedure
was repeated twice to yield an orange solid. Yield 86% (114 mg).
1H NMR (250 MHz, [D6]DMSO, 25 °C): δ = 7.98 (AAЈ, 12 H),
7.70 (BBЈ, 12 H), 6.30 (s, 6 H, 3-H, 6-H), 3.62 (s, 18 H, Me3N)
ppm. 13C NMR (62.9 MHz, [D6]DMSO, 25 °C): δ = 162.1,
146.0, 132.0, 125.4, 121.1, 113.4, 93.4, 88.3, 56.4 ppm.
C84H90I4N6O6Ti·4H2O (1901.19): calcd. C 53.07, H 4.87, N 4.42;
Bis(triethylammonium) Tris{4,5-bis[2-(4-nitrophenyl)ethynyl]-1,2-
benzenediolato}silicate(IV) (10): To a mixture of 1,2-dihydroxy-4,5-
bis[2-(4-nitrophenyl)ethynyl]benzene (8; 100 mg, 249 µmol) and
Et3N (16.2 mg, 124 µmol) in dry MeCN (10 mL) a 1 solution of
Si(MeO)4 (12.1 mg, 77.4 µmol) in dry MeCN was added. The solu-
tion turned orange and was stirred at room temperature for 24 h.
Overnight a solid precipitated which was filtered off, washed with
MeCN and dried in vacuo. Yield 78% (76.0 mg) of an orange solid.
1H NMR (250 MHz, [D6]DMSO, 25 °C): δ = 8.26 (AAЈ, 12 H),
7.73 (BBЈ, 12 H), 6.55 (s, 6 H, 3-H, 6-H), 3.06 (q, 12 H,
CH3CH2N), 1.16 (t, 18 H, CH3CH2N) ppm. 13C NMR (62.9 MHz,
[D6]DMSO, 295 K): δ = 154.6, 146.0, 131.7, 130.5, 124.1, 112.8,
111.9, 97.1, 88.9, 45.8, 8.8 ppm. C78H64N8O18Si (1429.5): calcd. C
65.54, H 4.51, N 7.84; found C 64.13, H 4.38, N 7.56. IR (KBr): ν
˜
= 3071 (w, C–H-aryl), 2197 (m, CϵC), 1591 (s, NO2), 1498 (s),
1384 (w), 1340 (s, NO2), 1244 (s, C–O), 1173 (vw), 1105 (w), 1073
(vw), 891 (w), 852 (w), 795 (w), 748 (w), 711 (vw), 687 (vw), 655
(w), 596 (vw), 565 (vw) cm–1.
found C 53.08, H 4.98, N 4.42. IR (KBr): ν = 3014 (vw, C–H-aryl),
˜
2955 (w, C–H), 2929 (w, C–H), 2885 (w, C–H), 2857 (w, N–Me),
2198 (w, CϵC), 1508 (w), 1479 (s), 1413 (w), 1369 (m), 1278 (w),
1244 (s, C–O), 1200 (w), 1113 (w), 1011 (vw), 955 (vw), 936 (w),
884 (w), 844 (m), 798 (w), 635 (m), 565 (m), 502 (m) cm–1.
1,2-Bis(tert-butyldimethylsilyloxy)-4,5-bis{2-[4-(dimethylamino)-
phenyl]ethynyl}benzene (12): To a mixture of 4,5-bis(tert-butyldime-
thylsilyloxy)-1,2-diiodobenzene (5; 189 mg, 320 µmol), (PPh3)2-
PdCl2 (24.0 mg, 34.2 µmol) and CuII (4.00 mg, 21.0 µmol) in dry
Et2NH (5 mL) (4-ethynylphenyl)dimethylamine (11; 100 mg,
680 µmol) was added. The red solution was heated to 50 °C for
24 h, cooled to room temperature and the solvent was evaporated
in vacuo. The remaining brown solid was purified by chromatog-
raphy on Al2O3 (neutral, act. V; dichloromethane/petroleum ether,
1:9) to yield a colourless solid. Yield 78% (156 mg) of a colourless
Acknowledgments
We thank the Deutsche Forschungsgemeinschaft for financial sup-
port. We also thank Heraeus GmbH and Wacker AG for support
with chemicals and Prof. Dr. J. Heck and Dr. C. Wittenburg (Insti-
tut für Anorganische Chemie, Universität Hamburg) for prelimi-
1
solid. H NMR (250 MHz, [D6]acetone, 25 °C): δ = 7.38 (AAЈ, 4
H), 6.99 (s, 2 H, 3-H, 6-H), 6.72 (BBЈ, 4 H), 2.99 (s, 12 H, Me2N), nary hyper-Rayleigh scattering measurements.
1.02 [s, 18 H, (CH3)3CSi], 0.28 [s, 12 H, (CH3)2Si] ppm. 13C NMR
(62.9 MHz, [D6]acetone, 25 °C): δ = 151.6, 148.0, 133.6, 124.7,
121.2, 113.1, 111.2, 94.5, 87.3, 40.5, 26.6, 19.4, –3.50 ppm.
C38H52N2O2Si2 (625.02): calcd. C 73.03, H 8.39, N 4.48; found C
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˜
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(w, C–H), 2929 (m, C–H), 2885 (w, C–H), 2857 (m, N–Me), 2199
(vw, CϵC), 1608 (s), 1523 (s), 1496 (w), 1362 (s), 1254 (m), 1187
(w), 1136 (w), 929 (m), 887 (vw), 861 (w), 840 (m), 816 (w), 782
(w) cm–1.
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Eur. J. Inorg. Chem. 2005, 4509–4515